CN112602208A - Electrode for all-solid battery and method of manufacturing electrode assembly including the same - Google Patents

Electrode for all-solid battery and method of manufacturing electrode assembly including the same Download PDF

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Publication number
CN112602208A
CN112602208A CN202080004673.8A CN202080004673A CN112602208A CN 112602208 A CN112602208 A CN 112602208A CN 202080004673 A CN202080004673 A CN 202080004673A CN 112602208 A CN112602208 A CN 112602208A
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electrode
active material
solid electrolyte
electrode active
material layer
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CN202080004673.8A
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CN112602208B (en
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郑慧利
崔洛永
韩惠恩
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Lg Energy Solution
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LG Chem Ltd
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    • H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
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    • H01M4/04—Processes of manufacture in general
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    • H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
    • H01M4/52—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of nickel, cobalt or iron
    • H01M4/525—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of nickel, cobalt or iron of mixed oxides or hydroxides containing iron, cobalt or nickel for inserting or intercalating light metals, e.g. LiNiO2, LiCoO2 or LiCoOxFy
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    • H01M4/583—Carbonaceous material, e.g. graphite-intercalation compounds or CFx
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    • H01M4/621—Binders
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Abstract

According to the present invention, it is possible to obtain an electrode of an all-solid battery having a low porosity, which uses a solid electrolyte material instead of a liquid electrolyte material and requires close contact between battery constituent materials such as an electrode active material and a solid electrolyte material, by adjusting the concentrations of a slurry forming an electrode active material layer and a slurry forming a solid electrolyte layer. When the manufacturing method according to the present disclosure is applied, the electrode active material layer is filled with the solid electrolyte material, thus enabling these constituent materials to be in close contact with each other, thereby improving the interface resistance characteristics.

Description

Electrode for all-solid battery and method of manufacturing electrode assembly including the same
Technical Field
This application claims the benefit of korean patent application No.10-2019-0057046, filed on 15.5.2019, to the korean intellectual property office, the disclosure of which is incorporated herein by reference in its entirety. The present disclosure relates to an electrode of an all-solid battery and a method of manufacturing an electrode assembly including the same.
Background
An all-solid battery using a solid electrolyte material has enhanced safety, prevents leakage of the electrolyte, allows improvement in reliability of the battery, and facilitates manufacture of a thin battery, as compared to a battery using a liquid electrolyte. In addition, since lithium metals are used as the anode, they have improved energy density, and thus, are expected to be used in high-capacity secondary battery applications for electric vehicles along with small-sized secondary batteries.
Since a solid electrolyte is used instead of a liquid electrolyte, the all-solid battery contains a large amount of a solid electrolyte material in electrodes including a positive electrode and a negative electrode to create an environment for movement of ions by impregnating the electrodes with the liquid electrolyte as in the liquid electrolyte battery, that is, to achieve ion conductivity similar to that of a battery using a liquid electrolyte.
In the case of an all-solid battery including a sulfide-based solid electrolyte as a solid electrolyte material, the interface resistance between the positive electrode/the solid electrolyte layer/the negative electrode greatly affects the cell resistance. In addition to the resistance between the layers, when the contact area between the electrolyte and the active material in each electrode is large, the interfacial resistance between the particles is low. Generally, an electrode is manufactured using a slurry having a high solid content, and a solid electrolyte layer is coated on the electrode. The electrode assembly is manufactured by applying an electrolyte layer and rolling the electrolyte layer, but the interfacial resistance is still high or the rolling is not good.
Disclosure of Invention
Technical problem
The present disclosure is designed to solve the above-described technical problems, and therefore, the present disclosure relates to an electrode of an all-solid battery in which the interfacial resistance between the electrode and an electrolyte separator is reduced, and a method of manufacturing an electrode assembly of the all-solid battery. These and other objects and advantages of the present disclosure will be understood by the following description. In addition, it will be readily understood that the objects and advantages of the present disclosure may be realized by means of the devices or methods described in the appended claims, and combinations thereof.
Technical scheme
The present disclosure is designed to solve the above-described technical problems. A first aspect of the present disclosure relates to a method of manufacturing an electrode of an all-solid battery, the method including the steps of: (S1) a first step of preparing a preliminary electrode active material layer forming slurry including an electrode active material and a solid electrolyte, wherein a concentration of solids other than a solvent in the slurry is 30 to 60% by weight, (S2) a second step of coating the preliminary electrode active material layer forming slurry on a surface of a current collector and drying the preliminary electrode active material layer forming slurry to form a preliminary electrode active material layer, (S3) a third step of preparing a solid electrolyte layer forming slurry including a solid electrolyte material, wherein a concentration of solids other than a solvent in the slurry is 30 to 50% by weight, and (S4) a fourth step of coating the solid electrolyte layer forming slurry on a surface of the preliminary electrode active material layer and drying the solid electrolyte layer forming slurry.
According to a second aspect of the present disclosure, in the first aspect, the preliminary electrode active material layer obtained in the second step has a porosity of 50 to 70 vol%.
According to a third aspect of the present disclosure, in the first or second aspect, the electrode obtained in the fourth step includes an electrode active material layer and a solid electrolyte layer formed on a surface of the electrode active material layer, and the electrode active material layer has a porosity of 20 to 30 vol%.
According to a fourth aspect of the present disclosure, in any one of the first to third aspects, the solid electrolyte material includes a sulfide-based solid electrolyte material.
According to a fifth aspect of the present disclosure, in the fourth aspect, the sulfide-based solid electrolyte contains sulfur (S) and includes at least one of Li-P-S (lps) -based glass or Li-P-S (lps) -based glass-ceramic.
According to a sixth aspect of the present disclosure, in at least one of the first to fifth aspects, the solvent comprises a non-polar solvent.
According to a seventh aspect of the present disclosure, in the sixth aspect, the nonpolar solvent includes at least one of 1, 2-dichlorobenzene, pentane, benzene, xylene, toluene, chloroform, hexane, cyclohexane, carbon tetrachloride, diethyl ether, diethylamine, dioxane, chlorobenzene, anisole, tetrahydrofuran, methyl tert-butyl ether, or heptane.
According to an eighth aspect of the present disclosure, in at least one of the first to seventh aspects, the preliminary electrode active material layer forming paste and/or the solid electrolyte layer forming paste includes a binder resin, and the binder resin includes at least one of an acrylate, an acrylonitrile-styrene-butadiene copolymer, a styrene-butadiene copolymer, an isobutylene-isoprene copolymer including butyl rubber, an acrylonitrile-butadiene-rubber (NBR), a Butadiene Rubber (BR), or an ethylene propylene diene terpolymer (EPDM).
A ninth aspect of the present disclosure relates to a method of manufacturing an all-solid battery, the method including the steps of: stacking a positive electrode and a negative electrode and applying pressure, wherein the negative electrode or at least one of the positive electrodes is defined in any one of the first to eighth aspects, and the positive electrode and the negative electrode are stacked with a solid electrolyte layer interposed therebetween.
A tenth aspect of the present disclosure is directed to an all-solid battery including a cathode, an anode, and a solid electrolyte separator interposed between the cathode and the anode, wherein at least one of the anode or the cathode is manufactured by the method according to any one of the first to eighth aspects.
Advantageous effects
The electrode and/or electrode assembly manufactured by the manufacturing method of the present disclosure may provide the following effects.
(1) The interfacial resistance between the electrode and the solid electrolyte membrane can be reduced.
(2) The interfacial resistance between the electrode active material and the solid electrolyte in the electrode can be reduced.
(3) The porosity in the electrode can be reduced.
(4) When the electrode and the electrode assembly manufactured by the manufacturing method of the present disclosure are applied to a battery, electrochemical properties of the battery, such as capacity, rate, and cycle performance, may be improved.
Drawings
The accompanying drawings illustrate preferred embodiments of the present disclosure and, together with the detailed disclosure, serve to provide a further understanding of the technical aspects of the disclosure, which should not be construed as being limited to the accompanying drawings. In the drawings, the shape, size, scaling or proportions of elements may be exaggerated for clarity of illustration.
Fig. 1a and 1b are schematic diagrams of a method of manufacturing an electrode of an all-solid battery according to a conventional technique, showing a preliminary electrode formed with high concentrations of a first paste and a second paste and an electrode of an all-solid battery.
Fig. 2a and 2b are schematic views of a method of manufacturing an electrode of an all-solid battery according to an embodiment of the present disclosure, illustrating a preliminary electrode formed using a first paste and a second paste and an electrode of an all-solid battery according to the present disclosure.
Detailed Description
Hereinafter, embodiments of the present disclosure will be described in detail. Before the description is made, it should be understood that the terms or words used in the specification and the appended claims should not be construed as limited to general or dictionary meanings, but interpreted based on the meanings and concepts corresponding to technical aspects of the present disclosure on the basis of the principle that the inventor is able to define terms appropriately for the best explanation. Therefore, the context of the embodiments described herein is merely the most preferred embodiment of the present disclosure and is not intended to fully describe the technical aspects of the present disclosure, so it should be understood that other equivalents and modifications may be made thereto at the time of filing this application.
Unless the context clearly indicates otherwise, when the term "comprising" is used in this specification, it indicates the presence of the stated elements, but does not preclude the presence or addition of one or more other elements.
The terms "about" and "substantially" are used herein in the sense given the manufacturing and material tolerances inherent in the described circumstances or nearly so, and are used to prevent an unscrupulous infringer from unfairly utilizing the disclosure in which exact or absolute numbers are set forth to facilitate an understanding of the disclosure.
The terminology used in the following detailed description is for the purpose of convenience and is not intended to be limiting. The terms "right," "left," "top," and "bottom" refer to the directions referenced in the drawings. The terms "inwardly" and "outwardly" refer to directions toward and away from the geometric center of a given device, system, and element thereof. The terms "front", "back", "upper", "lower" and related words and phrases refer to positions and orientations in the drawings and are not limiting. These terms include the above words, derivatives thereof and synonyms.
Unless the context clearly indicates otherwise, the temperature is expressed in degrees centigrade (° c), and the mixing ratio of each component is a weight ratio.
The present disclosure relates to a method of manufacturing an electrode of an all-solid battery. In addition, another embodiment of the present disclosure relates to a method of manufacturing an electrode assembly of an all-solid battery using the electrode manufactured by the manufacturing method of the present disclosure.
Fig. 2a and 2b schematically show a preliminary electrode and an electrode of an all-solid battery obtained according to an embodiment of the present disclosure. A method of manufacturing an electrode according to the present disclosure will be described in more detail with reference to fig. 2a and 2 b.
First, a preliminary electrode is obtained by forming a preliminary electrode active material layer on a surface of a current collector. In the present disclosure, an electrode having a preliminary electrode active material layer is referred to as a preliminary electrode.
In the present disclosure, the current collector may be, for example, a metal plate exhibiting electrical conductivity, and a current collector well known in the field of secondary batteries may be appropriately used according to the polarity of an electrode. For example, in the case of a negative electrode, a copper foil having an appropriate thickness may be used as a current collector, and in the case of a positive electrode, an aluminum foil may be used as a current collector.
Subsequently, a preliminary electrode active material layer is coated on the surface of the current collector to form a slurry (first slurry). The preliminary electrode active material layer forming paste is a liquid paste including an electrode active material and a solid electrolyte, and may also appropriately include a binder resin and a conductive material, if necessary.
In an embodiment of the present disclosure, the concentration of the remaining components (solids) in the first slurry other than the solvent is 30 to 60 wt%, preferably 30 to 55 wt%. When the concentration satisfies the above range, the first slurry may be uniformly coated on the current collector, and after drying, the preliminary electrode active material layer may exhibit appropriate porosity, and in the subsequent step, when the second slurry is coated, the second slurry may well enter the electrode active material layer. In the embodiments of the present disclosure, the solvent preferably includes at least one non-polar solvent of 1, 2-dichlorobenzene, pentane, benzene, xylene, toluene, chloroform, hexane, cyclohexane, carbon tetrachloride, diethyl ether, diethylamine, dioxane, chlorobenzene, anisole, tetrahydrofuran, methyl tert-butyl ether, or heptane.
In addition, at least one type of electrode active material may be appropriately selected according to the polarity of the electrode.
When the electrode is a positive electrode, the positive active material may include, but is not limited to, any type of positive active material of a lithium ion secondary battery. For example, the positive active material may include, for example, lithium cobalt oxide (LiCoO)2) And lithium nickel oxide (LiNiO)2) Such layered compounds or compounds having one or more transition metal substitutions; chemical formula Li1+xMn2- xO4(x is 0 to 0.33), LiMnO3、LiMn2O3、LiMnO2The lithium manganese oxide of (1); lithium copper oxide (Li)2CuO2) (ii) a Such as LiV3O8、LiV3O4、V2O5And Cu2V2O7Such a vanadium oxide; from the formula LiNi1-xMxO2A nickel-site type lithium nickel oxide (Ni-site type lithium nickel oxide) represented by (M ═ at least one selected from Co, Mn, Al, Cu, Fe, Mg, B, and Ga, and x ═ 0.01 to 0.3), for example, LiNi0.8Mn0.1Co0.1O2(ii) a Represented by the chemical formula LiMn1-xMxO2(M ═ Co, Ni, Fe, Cr, Zn or Ta, x ═ 0.01 to 0.1) or Li2Mn3MO8Lithium manganese complex oxides represented by (M ═ Fe, Co, Ni, Cu, or Zn); from LiNixMn2-xO4A spinel-structured lithium manganese composite oxide represented by; LiMn in which Li in the formula is partially substituted with alkaline earth metal ions2O4(ii) a A disulfide compound; fe2(MoO4)3. However, the positive electrode active material is not limited thereto.
In contrast, when the electrode is an anode, the anode active material may include a carbon-based material. The carbon-based material may be at least one selected from the group consisting of graphite such as crystalline artificial graphite and/or crystalline natural graphite, amorphous hard carbon, low-crystallinity soft carbon, carbon black, acetylene black, graphene, and fibrous carbon. Preferably, the carbon-based material may include crystalline artificial graphite and/or crystalline natural graphite. In addition, the negative active material may include any type of negative active material that may be used in an all-solid battery. For example, negative electrode activityThe material may also include a metal selected from lithium; such as LixFe2O3(0≤x≤1)、LixWO2(0≤x≤1)、SnxMe1-xMe’yOz(Me: Mn, Fe, Pb, Ge; Me': Al, B, P, Si, elements of groups I, II and III of the periodic Table of the elements, halogen; 0<x is less than or equal to 1; y is more than or equal to 1 and less than or equal to 3; z is more than or equal to 1 and less than or equal to 8); a lithium alloy; a silicon-based alloy; a tin-based alloy; such as SnO, SnO2、PbO、PbO2、Pb2O3、Pb3O4、Sb2O3、Sb2O4、Sb2O5、GeO、GeO2、Bi2O3、Bi2O4And Bi2O5Such metal oxides; conductive polymers such as polyacetylene; a Li-Co-Ni-based material; titanium oxide; at least one of lithium titanium oxide.
In the embodiment of the present disclosure, the amount of the electrode active material may be 30 to 90 wt%, and preferably 40 to 80 wt%, based on 100 wt% of the finally obtained electrode active material layer.
The solid electrolyte preferably includes a sulfide-based solid electrolyte. In an embodiment of the present disclosure, the solid electrolyte may include at least one of a polymer-based solid electrolyte or an oxide-based solid electrolyte within a necessary range.
In the embodiment of the present disclosure, the amount of the solid electrolyte may be 10 to 70 wt%, and preferably 10 to 50 wt% based on 100 wt% of the finally obtained electrode active material layer in terms of ionic conductivity.
The sulfide-based solid electrolyte material includes sulfur (S) and has an ionic conductivity of a metal belonging to group I or group II of the periodic table, and may include Li-P-S-based glass or Li-P-S-based glass ceramic. Non-limiting examples of the sulfide-based solid electrolyte may include Li2S-P2S5、Li2S-LiI-P2S5、Li2S-LiI-Li2O-P2S5、Li2S-LiBr-P2S5、Li2S-Li2O-P2S5、Li2S-Li3PO4-P2S5、Li2S-P2S5-P2O5、Li2S-P2S5-SiS2、Li2S-P2S5-SnS、Li2S-P2S5-Al2S3、Li2S-GeS2Or Li2S-GeS2-at least one of ZnS. However, the sulfide-based solid electrolyte is not particularly limited thereto.
The polymer-based solid electrolyte is a composition of a lithium salt and a polymer resin (i.e., a polymer electrolyte material formed by adding a polymer resin to a solvated lithium salt), and may exhibit about 1 × 10-7Ion conductivity of S/cm or more, and preferably 1X 10-5S/cm or greater.
Non-limiting examples of the polymer resin may include at least one of polyether-based polymers, polycarbonate-based polymers, acrylate-based polymers, polysiloxane-based polymers, phosphazene-based polymers, polyethylene derivatives, alkylene oxide derivatives such as polyethylene oxide, phosphate ester polymers, poly agitated lysine, polyester sulfide, polyvinyl alcohol, polyvinylidene fluoride, or polymers including ion dissociable groups. In addition, in the polymer electrolyte, the polymer resin may include, for example, at least one selected from a branched copolymer, a comb-like polymer resin, and a cross-linked polymer resin obtained by copolymerizing a comonomer of an amorphous polymer such as PMMA, polycarbonate, polysiloxane (pdms), and/or phosphazene into a main chain of polyethylene oxide (PEO).
In the electrolyte of the present disclosure, the lithium salt is an ionizable lithium salt and may be represented as Li+X-. The anion of the lithium salt is not particularly limited and may include, for example, F-、Cl-、Br-,I-、NO3 -,N(CN)2 -、BF4 -、ClO4 -、PF6 -、(CF3)2PF4 -、(CF3)3PF3 -、(CF3)4PF2 -、(CF3)5PF-、(CF3)6P-、CF3SO3 -、CF3CF2SO3 -、(CF3SO2)2N-、(FSO2)2N-、CF3CF2(CF3)2CO-、(CF3SO2)2CH-、(SF5)3C-、(CF3SO2)3C-、CF3(CF2)7SO3 -、CF3CO2 -、CH3CO2 -、SCN-、(CF3CF2SO2)2N-。
The oxide-based solid electrolyte material contains oxygen (O) and has an ionic conductivity of a metal belonging to group I or II of the periodic table. Non-limiting examples of the oxide-based solid electrolyte material may include materials selected from the group consisting of LLTO-based compounds, Li6La2CaTa2O12、Li6La2ANb2O12(A is Ca or Sr), Li2Nd3TeSbO12、Li3BO2.5N0.5、Li9SiAlO8Such as Li1.5Al0.5Ge1.5(PO4)3Such LAGP-based compound, LATP-based compound and Li1+xTi2-xAlxSiy(PO4)3-y(0≤x≤1,0≤y≤1)、LiAlxZr2-x(PO4)3(0≤x≤1,0≤y≤1)、LiTixZr2-x(PO4)3(x is more than or equal to 0 and less than or equal to 1, y is more than or equal to 0 and less than or equal to 1), and at least one of LISICON compounds, LIPON compounds, perovskite compounds, NASICON compounds or LLZO compounds. However, the oxide-based solid electrolyte is not particularly limitedBut are not limited thereto.
The binder resin may include, but is not limited to, any type that is electrochemically stable. For example, the binder resin may include polyvinylidene fluoride-hexafluoropropylene copolymer, polyvinylidene fluoride-trichloroethylene copolymer, acrylic ester, polymethyl methacrylate, polyacrylonitrile, polyvinylpyrrolidone, polyvinyl acetate, polyethylene-vinyl acetate copolymer, polyethylene oxide, cellulose acetate butyrate, cellulose acetate propionate, cyanoethyl pullulan, cyanoethyl polyvinyl alcohol, cyanoethyl cellulose, cyanoethyl sucrose, pullulan, carboxymethyl cellulose, acrylonitrile-styrene-butadiene copolymer, polyimide, styrene-butadiene copolymer, isobutylene-isoprene copolymer such as butyl rubber, acrylonitrile-butadiene-rubber (NBR), Butadiene Rubber (BR), or ethylene propylene diene terpolymer (EPDM). In the embodiment of the present disclosure, when considering the use of the sulfide-based solid electrolyte and the nonpolar solvent in preparing the electrode active material layer forming slurry, the binder resin preferably includes a nonpolar binder resin. The non-polar binder resin may include at least one of an acrylate, an acrylonitrile-styrene-butadiene copolymer, a styrene-butadiene copolymer, an isobutylene-isoprene copolymer such as butyl rubber, an acrylonitrile-butadiene-rubber (NBR), or an ethylene propylene diene terpolymer (EPDM).
The binder resin may be generally included in a range of 1 to 10 wt% based on 100 wt% of the electrode active material layer.
In the present disclosure, the amount of the conductive material is generally 1 to 10% by weight based on the total weight of the mixture including the electrode active material. The conductive material is not limited to a specific type, and may include a conductive material having conductivity without causing a chemical change in a corresponding battery, for example, at least one selected from the group consisting of: graphite such as natural graphite or artificial graphite; carbon black such as carbon black, acetylene black, ketjen black, channel black, furnace black, lamp black and thermal black; conductive fibers including carbon fibers such as Vapor Grown Carbon Fibers (VGCF) or metal fibers; metal powders such as fluorocarbon, aluminum, and nickel powders; conductive whiskers such as zinc oxide and potassium titanate; conductive metal oxides such as titanium oxide; conductive materials such as polyphenylene derivatives.
In the present disclosure, each electrode active material layer may include at least one type of additive among an oxidation stabilizer, a reduction stabilizer, a flame retardant, a heat stabilizer, or an antifogging agent, if necessary.
When the first slurry is prepared as described above, the first slurry is coated on at least one surface of the current collector and dried to form a preliminary electrode active material layer. In this case, the method of applying the first paste is not limited to a specific type, and may include, for example, blade coating, dip coating, gravure coating, slot die coating, spin coating, comma coating, bar coating, reverse roll coating, screen coating, and cap coating methods.
Subsequently, the coated first slurry is dried to remove the solvent.
In the present disclosure, the porosity of the preliminary electrode active material layer obtained after drying is preferably about 50 to 70 vol%. In the present disclosure, it is possible to obtain a composite electrode including a plurality of components each having a true specific gravity and a supported amount per unit area (g/m) thereof2) And preparing the thickness of the electrode active material layer to calculate the porosity. When the porosity is less than the above range, as described below, the solid electrolyte layer forming slurry (second slurry) does not sufficiently enter the preliminary electrode active material layer when the solid electrolyte layer is applied, which makes it impossible to form the electrode active material layer having a desired level of porosity. In contrast, when the porosity exceeds the above range, the adhesive strength between the electrode active material layer and the current collector may be reduced. That is, when the porosity range is satisfied, the adhesive strength of the electrode active material layer and the current collector may be maintained in a desired range, and the second slurry may smoothly enter the preliminary electrode active material layer in the following step, so that the electrode active material layer may be filled with the solid electrolyte.
In the present disclosure, the porosity of the preliminary electrode active material layer may be controlled by adjusting the concentration of the first slurry. Fig. 2a is a schematic view of a preliminary electrode obtained according to an embodiment of the present disclosure, showing a preliminary electrode active material layer 100 formed on a surface of a current collector 200. The preliminary electrode active material layer includes a solid electrolyte material 120 and an electrode active material 110, and at least a portion of a surface of the electrode active material may be coated with the solid electrolyte material. As shown in fig. 2a, a preliminary electrode active material layer having a porosity of about 50 to 70 vol% may be obtained by controlling the concentration of solids in the first slurry within the above-described range. Fig. 1a is a schematic view of a preliminary electrode formed with a high concentration of the first slurry as in the comparative example, showing a preliminary electrode active material layer 10 formed on the surface of a current collector 20. The preliminary electrode active material layer includes the solid electrolyte material 12 and the electrode active material 11, and at least part of the surface of the electrode active material may be coated with the solid electrolyte material. As shown in fig. 1a, the concentration of solids in the first slurry is high, and as a result, the porosity is lower than that of the preliminary electrode active material layer obtained in the present disclosure.
Subsequently, a solid electrolyte layer forming slurry (second slurry) is coated on the preliminary electrode active material layer and dried to form an electrode active material layer and a solid electrolyte layer on a surface of the electrode active material layer. The second slurry is a liquid slurry comprising a solid electrolyte. In the embodiment of the present disclosure, the slurry may further include a binder resin in an appropriate range, if necessary. For example, the binder resin may be included in a range of 1 to 20 parts by weight based on 100 parts by weight of the solid electrolyte.
In an embodiment of the present disclosure, the concentration of the remaining components (solids) in the second slurry other than the solvent is 30 to 50 wt%, preferably 30 to 40 wt%. When the concentration satisfies the above range, an optimal amount of the second slurry may enter the preliminary electrode active material layer to fill the pores of the preliminary electrode active material layer and form a solid electrolyte layer of a predetermined thickness on the surface of the electrode active material layer. In addition, the formation of the solid electrolyte layer having a predetermined thickness may provide sufficient adhesion between the corresponding electrode and the counter electrode. In the present disclosure, with respect to the components (solid electrolyte, binder resin, and the like) included in the second paste, reference may be made to the description of preparing the electrode active material layer forming paste. For example, at least one of the above components may be appropriately selected and used to prepare the second slurry.
As described above, when the second slurry is prepared, the second slurry is coated on the surface of the preliminary electrode active material layer obtained in the above-described step and dried to form the electrode active material layer and the solid electrolyte layer on the surface of the electrode active material layer. In this case, the method of applying the slurry is not limited to a specific type, and may include, for example, blade coating, dip coating, gravure coating, slot die coating, spin coating, comma coating, bar coating, reverse roll coating, screen coating, and cap coating methods. Subsequently, the coated solid electrolyte layer forming slurry is dried to remove the solvent.
As described above, when the second slurry is coated on the surface of the preliminary electrode active material layer having a high porosity, the second slurry enters into the preliminary electrode active material layer through the pores of the preliminary electrode active material layer and fills the pores of the electrode active material. The resulting electrode active material layer may have a low level of porosity, for example, preferably 10 to 30 volume% or 20 to 30 volume% porosity.
Fig. 2b is a diagram of an electrode of an all-solid battery manufactured according to an embodiment of the present disclosure, schematically illustrating a solid electrolyte layer 300 formed on an electrode active material layer 100. Referring to fig. 2b, when the second paste is coated, the second paste enters into the preliminary electrode active material layer having low porosity, and the pores of the preliminary electrode active material layer are filled with the solid electrolyte material, thereby obtaining an electrode having low porosity.
Fig. 1b is a diagram of an electrode of an all-solid battery manufactured according to a comparative example, schematically illustrating a solid electrolyte layer 30 formed on an electrode active material layer 10. Referring to fig. 1b, when the second paste is applied, the high porosity of the preliminary electrode active material layer hinders the second paste from entering into the preliminary electrode active material layer, which makes it difficult to fill the pores of the preliminary electrode active material layer with the solid electrolyte material. Therefore, it is difficult to manufacture an electrode having low porosity.
As described above, the present disclosure can obtain an electrode of an all-solid battery having low porosity by adjusting the concentration of the slurry. All-solid batteries use a solid electrolyte material instead of a liquid electrolyte material, and therefore require close contact between constituent materials of the battery, such as an electrode active material, and the solid electrolyte material. Therefore, when the manufacturing method according to the present disclosure is applied, the electrode active material layer is filled with the solid electrolyte material so that the components are brought into close contact, thereby improving the interface resistance characteristics.
After obtaining the electrodes, a pressing process (first pressing process) may be additionally performed on the electrodes as necessary before manufacturing the electrode assembly. However, since the electrode obtained as described above exhibits low porosity, pressing can be performed under very mild conditions.
The electrode having the solid electrolyte layer may be prepared by the above-described method. An electrode according to the present disclosure includes an electrode active material layer and a solid electrolyte layer formed on a surface of the electrode active material layer. The solid-state electrode active material layer has a mixed phase of the solid electrolyte and the electrode active material, and the mixed phase includes some derived from the first slurry and some introduced through the second slurry. When manufacturing an electrode of an all-solid battery, an electrode having an appropriate porosity necessary for a solid electrolyte battery can be obtained by appropriately controlling the concentrations of the first paste and the second paste without applying too much pressure. The electrode may further include a current collector.
In addition, the present disclosure provides an electrode assembly of an all-solid battery. An electrode assembly of an all-solid battery may include a positive electrode, a negative electrode, and a solid electrolyte separator interposed between the positive electrode and the negative electrode. In this case, at least one of the negative electrode or the positive electrode may be an electrode obtained by the manufacturing method according to the present disclosure. In the embodiment of the present disclosure, the electrode assembly may be manufactured by stacking the cathode and the anode and applying pressure to join the cathode and the anode if necessary. In this case, since the surface of at least one electrode has the solid electrolyte layer, the solid electrolyte layer may serve as a solid electrolyte membrane. Alternatively, the electrode assembly may be manufactured by forming a separate solid electrolyte membrane, placing it between the positive electrode and the negative electrode, and applying pressure to join the negative electrode, the positive electrode, and the solid electrolyte membrane, if necessary. In the embodiments of the present disclosure, the porosity of the electrode may be further adjusted to a desired level by a pressing process (second pressing process) additionally performed when the electrode assembly is manufactured. The solid electrolyte separator may include, but is not limited to, any ionically conductive layer including solid electrolyte materials that would be commonly used in the art of all-solid batteries. For example, in the solid electrolyte membrane, the solid electrolyte material may include at least one of a polymer-based solid electrolyte material, an oxide-based solid electrolyte material, or a sulfide-based solid electrolyte material.
In certain embodiments of the present disclosure, the first pressing process or the second pressing process or both may be performed, and the pressing process may be appropriately performed, so that the electrode included in the all-solid battery may eventually have a porosity of less than about 10 vol%. For example, both the first pressing process and the second pressing process may be performed in this order so that the electrode may eventually have a porosity of less than 10 vol%, or only the second pressing process may be performed without performing the first pressing process so that the electrode may eventually have a porosity of less than 10 vol%. However, since the electrode obtained as described above has a low porosity, pressing can be performed under very mild conditions.
In still another embodiment, when both the positive electrode and the negative electrode are the electrodes manufactured by the manufacturing method of the present disclosure, both the positive electrode and the negative electrode have the solid electrolyte layer on the surface of the electrode active material layer, and the two electrodes may be stacked such that the solid electrolyte layers of the two electrodes face each other and are laminated to obtain an electrode assembly of an all-solid battery including the positive electrode/the solid electrolyte separator/the negative electrode. That is, the solid electrolyte layers of the two electrodes may be combined to form a solid electrolyte membrane.
In addition, the present disclosure provides a battery module including the electrode assembly, a battery pack including the battery module, and a device including the battery pack as a power source. In this case, specific examples of the device may include, but are not limited to, a power storage system operated by power from an electric motor, an electric tool, an electric vehicle (including an Electric Vehicle (EV), a Hybrid Electric Vehicle (HEV), a plug-in hybrid electric vehicle (PHEV)), an electric two-wheeled vehicle (including an electric bicycle and an electric scooter), and an electric golf cart.
Hereinafter, the present disclosure is described in more detail by way of examples, but the following examples are provided to describe the present disclosure by way of illustration, and the scope of the present disclosure is not limited thereto.
Preparation example
(1) Preparation of electrode assemblies
An aluminum thin film (17 μm thick) was prepared as a positive current collector, and a copper thin film (17 μm thick) was prepared as a negative current collector.
As shown in the following [ table 1], a positive electrode active material, a solid electrolyte, a binder, and a conductive material were added to xylene and mixed together using a paste mixer to prepare a first slurry for a positive electrode. Mix at 1500rpm for 15 minutes at room temperature. The components are summarized in the following [ table 1 ]. The concentration of solids in each first slurry is shown below in [ table 2 ].
In addition, as shown in [ table 1] below, an anode active material, a solid electrolyte, a binder, and a conductive material were added to xylene and mixed together using a paste mixer to prepare a first slurry for an anode. Mix at 1500rpm for 15 minutes at room temperature. The components are summarized in the following [ table 1 ]. The concentration of solids in each second slurry is shown below in table 2.
Subsequently, each of the first slurries was coated on a current collector using a doctor blade and vacuum-dried at room temperature for 2 hours to form a preliminary electrode active material layer. The porosity of each preliminary electrode active material layer is as shown in [ table 2] below.
Subsequently, the LPS solid electrolyte and binders (BR and NBR) were added to xylene and mixed together. The weight ratio of the solid electrolyte to the binder was 95: 5. The solid electrolyte and the binder are mixed using a paste mixer to prepare a second slurry. The prepared second slurry was coated on the preliminary electrode active material layer at a coating rate of 5 m/min using a doctor blade and vacuum-dried at room temperature for 12 hours. The porosity of each preliminary electrode active material layer is as shown in [ table 2] below.
Each of the positive and negative electrodes obtained as described above was used and stacked with lithium metal (40 μm thick) in opposite polarity, and a pressure of 400Mpa was applied at room temperature for 1 minute to manufacture a battery.
Materials and characteristics used in each example and comparative example are shown in [ table 1] below.
[ Table 1]
Figure BDA0002948234050000121
[ Table 2]
Figure BDA0002948234050000122
[ Table 3]
Figure BDA0002948234050000131
1) Capacity efficiency measuring method
The batteries manufactured in example 1 and comparative example 1 were charged and discharged at 25 ℃ with a constant current of 0.05C in one cycle in a voltage range of 3V to 4.25V as compared to lithium metal, and the battery capacity (actual capacity) compared to the design capacity was observed. In addition, the batteries manufactured in example 2 and comparative example 2 were charged and discharged at 25 ℃ with a constant current of 0.05C in one cycle in a voltage range of 0.005V to 1.5V as compared to lithium metal, and the battery capacity as compared to the design capacity was observed.
2) Method for evaluating high rated discharge characteristics
In contrast to lithium metal, the batteries of example 1 and comparative example 1 were charged and discharged at a constant current of 0.05C at 25 ℃ in one cycle in a voltage range of 3V to 4.25V, and the battery capacity (first cycle) was observed. Subsequently, the battery was charged and discharged at a constant current of 0.1C in another cycle in a voltage range of 3V to 4.25V, and the battery capacity was observed (second cycle). On the other hand, the batteries of example 2 and comparative example 2 were charged and discharged at 25 ℃ with a constant current of 0.05C in one cycle in a voltage range of 0.005V to 1.5V, as compared to lithium metal, and the battery capacity (first cycle) was observed. Subsequently, the battery was charged and discharged at a constant current of 0.1C in another cycle in a voltage range of 0.005V to 1.5V, and the battery capacity was observed (second cycle). In each example and comparative example, the battery capacity ratio at the first cycle/second cycle was observed and shown in [ table 3] above.
3) Evaluation of
As can be seen from the above [ table 3], the actual capacities of the batteries of examples 1 and 2 were found to be closer to the design capacity than the batteries of comparative examples. It can also be seen that the batteries according to examples 1 and 2 have better high rated discharge characteristics than the battery of the comparative example.

Claims (10)

1. A method of manufacturing an electrode for an all-solid battery, the method comprising the steps of:
(S1) a first step of preparing a preliminary electrode active material layer forming slurry including an electrode active material and a solid electrolyte, wherein a concentration of solids other than a solvent in the slurry is 30 to 60 wt%;
(S2) a second step of coating the preliminary electrode active material layer forming slurry on a surface of a current collector and drying the preliminary electrode active material layer forming slurry to form a preliminary electrode active material layer;
(S3) a third step of preparing a solid electrolyte layer forming slurry including a solid electrolyte material, wherein a concentration of solids other than a solvent in the slurry is 30 to 50 wt%; and
(S4) a fourth step of coating the solid electrolyte layer forming slurry on the surface of the preliminary electrode active material layer and drying the solid electrolyte layer forming slurry.
2. The method of manufacturing an electrode for an all-solid battery according to claim 1, wherein the preliminary electrode active material layer obtained in the second step has a porosity of 50 to 70 vol%.
3. The method of manufacturing an electrode for an all-solid battery according to claim 1, wherein the electrode obtained in the fourth step includes an electrode active material layer and a solid electrolyte layer formed on a surface of the electrode active material layer, and the electrode active material layer has a porosity of 20% by volume to 30% by volume.
4. The method of manufacturing an electrode for an all-solid battery according to claim 1, wherein the solid electrolyte material includes a sulfide-based solid electrolyte material.
5. The method of manufacturing an electrode for an all-solid battery according to claim 4, wherein the sulfide-based solid electrolyte contains sulfur S and includes at least one of Li-P-S LPS-based glass or Li-P-S LPS-based glass ceramic.
6. The method of manufacturing an electrode for an all-solid battery according to claim 1, wherein the solvent comprises a nonpolar solvent.
7. The method of manufacturing an electrode for an all-solid battery according to claim 6, wherein the nonpolar solvent comprises at least one of 1, 2-dichlorobenzene, pentane, benzene, xylene, toluene, chloroform, hexane, cyclohexane, carbon tetrachloride, diethyl ether, diethylamine, dioxane, chlorobenzene, anisole, tetrahydrofuran, methyl tert-butyl ether, or heptane.
8. The method of manufacturing an electrode for an all-solid battery according to claim 1, wherein the preliminary electrode active material layer forming slurry and/or the solid electrolyte layer forming slurry includes a binder resin, and
the binder resin includes at least one of acrylate, acrylonitrile-styrene-butadiene copolymer, isobutylene-isoprene copolymer including butyl rubber, acrylonitrile-butadiene-rubber NBR or ethylene propylene diene terpolymer EPDM.
9. A method of manufacturing an all-solid battery, the method comprising the steps of:
the positive electrode and the negative electrode are stacked and pressure is applied,
wherein at least one of the anode or the cathode is defined according to any one of claims 1 to 8, and the cathode and the anode are stacked with a solid electrolyte layer interposed therebetween.
10. An all-solid battery comprising a positive electrode, a negative electrode, and a solid electrolyte separator interposed between the positive electrode and the negative electrode, wherein at least one of the negative electrode or the positive electrode is manufactured by the method according to any one of claims 1 to 8.
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